Composition comprising at least one first semi-crystalline polymer and at least one second film-forming polymer

ABSTRACT

The invention relates to a composition comprising, in a physiologically acceptable medium, at least one first semi-crystalline polymer having a melting point of greater than or equal to 30° C., and at least one second film-forming polymer capable of forming a hydrophobic film at room temperature. The composition makes it possible to obtain a film that is more resistant to removal by cold water than to removal by warm water. The composition can be applied to the making up and care of keratin materials.

The present invention relates to a cosmetic composition comprising atleast one semi-crystalline polymer and a polymer capable of forming ahydrophobic film, which can be used as a makeup or care composition fora keratin material such as the skin, the eyelashes, the eyebrows, thehair and the nails, of human beings. The invention also relates to acosmetic makeup or care process for a keratin material.

The composition may be in the form of a mascara, an eyeliner, a productfor the lips, a face powder, an eyeshadow, a foundation, a makeupproduct for the body, a concealer product, a product for the nails, anantisun composition, a skin coloring composition or a skincare product.For example, the invention relates to a mascara.

Mascara compositions in the form of a wax-in-water emulsion comprisingsurfactants are known from WO-A-95/15741. However, the makeup filmobtained with these compositions does not always show good waterresistance, and when the film comes into contact with water, for examplewhen bathing or taking a shower, it can partially disintegrate by beingworn away or by spreading around the eyes. The wearing away of the filmgives rise to a substantial reduction in the intensity of the color ofthe makeup, thus obliging the consumer to freshen the application of themascara. As regards the spreading of the film, this forms a veryunsightly aureole around the area to which makeup has been applied.Tears and perspiration also cause these same drawbacks.

To promote the water resistance of makeup, it is known practice fromU.S. Pat. No. 4,423,031 to use acrylic polymers in aqueous dispersion.However, the mascara may be difficult to remove and may require the useof special makeup removers based on oils or on organic solvents. Suchmakeup removers may irritate the eyes, they may in particular causestinging or they may leave a veil over the eyes, or alternatively theymay leave an uncomfortable greasy residual film on the skin around theeyes (eyelids).

To avoid the use of these special makeup removers, it is possible to usesoap and water, as disclosed in WO-A-96/33690, by proposing a mascaracomprising a water-insoluble polymer and a water-soluble film-formingpolymer. However, the use of soap may cause eye discomfort due tostinging or to the deposition of a veil over the eyes. Soap alsodissolves the film of makeup, which then spreads around the eyes andforms unsightly aureoles and stains the skin.

The use of warm water, for example water with a temperature above orequal to 35° C. (temperature measured at atmospheric pressure), such asranging from about 35° C. to 50° C., makes it possible to avoid at leastone of the drawbacks of the makeup removers known, but thecold-water-resistant mascara compositions described previously cannot beremoved with warm water.

An aspect of the present invention is a cosmetic composition that can beremoved with warm water while at the same time having improvedcold-water resistance.

The inventor has discovered that such a composition may be obtainedusing at least one film-forming polymer capable of forming a hydrophobicfilm and at least one specific semi-crystalline polymer. After applyingthe composition to a keratin material, such as the eyelashes, the makeupobtained shows improved resistance to removal by cold water, that is tosay to water with a temperature below or equal to 30° C., for examplewhen bathing, and/or to tears and/or to perspiration, compared toresistance to removal in the presence of warm water. The makeup is thusmore easily removed with warm water, such as by rubbing with cotton woolor gauze: the makeup detaches easily from the eyelashes and can beremoved from the eyelashes without fragmenting (in the form of a sheath)or in the form of fragments or pieces. The makeup thus removed does notspread on the skin, which avoids the formation of aureoles around theeyes; the skin is not stained when removing the makeup and remainsclean. The makeup is removed more simply with warm water, including warmwater containing no detergent such as soaps. For the makeup removal, thewarm water used may be tap water, demineralized water or mineral waterbrought to a temperature of greater than or equal to 35° C., forexample, from about 35° C. to 50° C.

According to one aspect of the invention, there is provided acomposition comprising, in a physiologically acceptable medium, at leastone first semi-crystalline polymer with a melting point of greater thanor equal to 30° C., and at least one second film-forming polymer capableof forming a hydrophobic film at room temperature.

Another aspect of the invention is the use of a composition as definedabove to obtain a film applied to a keratin material, the film beingresistant to cold water and/or removable with warm water.

A further aspect of the invention is a cosmetic makeup or care processfor a keratin material, comprising the application of a composition asdefined above to the keratin material.

Yet another aspect of the invention is the use of a firstsemi-crystalline polymer with a melting point of greater than or equalto 30° C., and at least one second film-forming polymer capable offorming a hydrophobic film at room temperature, in a cosmetic makeup orcare composition for a keratin material, to obtain a film applied to thekeratin material that is resistant to cold water and/or that can beremoved with warm water.

Another aspect of the invention is also a cosmetic process for removingmakeup from a keratin material made up with a composition as definedabove, comprising rinsing the said made-up keratin material at leastonce with warm water maintained at a temperature of greater than orequal to 35° C.

One aspect of the invention is a composition comprising, in aphysiologically acceptable medium, at least one first semi-crystallinepolymer having a melting point of greater than or equal to 30° C., andat least one second film-forming polymer that is capable of forming ahydrophobic film at room temperature.

Another aspect of the invention is a mascara comprising, in aphysiologically acceptable medium, at least one first semi-crystallinepolymer with a melting point of greater than or equal to 30° C., and atleast one second film-forming polymer capable of forming a hydrophobicfilm at room temperature.

Another aspect of the invention is a process for making a filmcomprising including in a cosmetic makeup or care composition for akeratin material at least one first semi-crystalline polymer with amelting point of greater than or equal to 30° C. and at least one secondfilm-forming polymer capable of forming a hydrophobic film at roomtemperature; wherein said film is applied to said keratin material andis more resistant to removal by cold water than to removal by warm waterhaving a temperature of at least 35° C.

Another aspect of the invention is a composition comprising, in aphysiologically acceptable medium, at least one first semi-crystallinepolymer having a melting point of greater than or equal to 30° C., andat least one second film-forming polymer that is capable of forming ahydrophobic film at room temperature; wherein said at least onesemi-crystalline polymer does not comprise a polysaccharide backbone.

Yet another aspect of the invention is a composition comprising, in aphysiologically acceptable medium, at least one first semi-crystallinepolymer having a melting point of greater than or equal to 30° C., andat least one second film-forming polymer that is capable of forming ahydrophobic film at room temperature; wherein said semi-crystallinepolymer is not polycaprolactone.

In accordance with the present invention, the expression“physiologically acceptable” should be understood as meaning a mediumthat is compatible with a keratin material, such as a cosmetic medium.According to one aspect, the composition according to the inventioncontains little emulsifier (surfactant), or is even free of emulsifier;for example, the emulsifier is present in an amount of less than 0.5% byweight relative to the total weight of the composition. The compositionhas good resistance to cold water.

In accordance with the present invention, the term “emulsifier” meansany amphiphilic compound chosen from nonionic amphiphilic compounds withan HLB (hydrophilic-lipophilic balance) of greater than or equal to 10,and ionic amphiphilic compounds whose hydrophilic portion comprises acounterion with a molar mass of greater than or equal to 50 g/mol.

The makeup removal with warm water is obtained using at least onesemi-crystalline polymer with a thermal transition corresponding to itsmelting point.

Above its melting point, the semi-crystalline polymer, after its changeof state, makes the film more water-sensitive: the film of makeup ismade brittle on contact with warm water and by rubbing it, for examplewith the fingers or with a cloth or cotton wool, the film disintegratesreadily or detaches from its support.

The at least one semi-crystalline polymer may be present in thecomposition in an amount ranging from 0.1% to 30% by weight, for examplefrom 0.5% to 25% by weight. According to another embodiment, thesemi-crystalline polymer is present in an amount ranging from 1% to 20%by weight, such as from 3% to 15% by weight, relative to the totalweight of the composition.

In accordance with the present invention, the term “polymers” meanscompounds comprising at least two repeating units, such as, at leastthree repeating units. According to another aspect, the compoundscomprise at least ten repeating units.

In accordance with the present invention, the expression“semi-crystalline polymer” means polymers comprising a crystallizableportion, crystallizable pendent chain, or crystallizable block in theskeleton, and an amorphous portion in the skeleton and having atemperature of first-order reversible phase change, for example ofmelting (solid-liquid transition). When the crystallizable portion is inthe form of a crystallizable block of the polymer skeleton, theamorphous portion of the polymer is in the form of an amorphous block;in this case, the semi-crystalline polymer is a block copolymer, forexample of the diblock, triblock or multiblock type comprising at leastone crystallizable block and at least one amorphous block. The term“block” generally means at least five identical repeating units. Thecrystallizable block(s) is (are) then of different chemical nature fromthe amorphous block(s).

The semi-crystalline polymer according to the invention has a meltingpoint of greater than or equal to 30° C., for example a melting pointranging from a 30° C. to 80° C., According to another aspect, themelting point ranges from 30° C. to 60° C. This melting point is atemperature of first-order change of state.

This melting point may be measured by any known method, for example byusing a differential scanning calorimeter (DSC).

According to one aspect, the semi-crystalline polymer(s) referred to inthe invention have a number-average molecular mass greater than or equalto 1,000.

According to another aspect, the semi-crystalline polymer(s) in thecomposition of the invention have a number-average molecular mass{overscore (M)}n ranging from 2,000 to 800,000, for example from 3,000to 500,000, and also from 4,000 to 150,000. According to another aspect,the number-average molecular mass ranges from less than 100,000, forexample, from 4,000 to 99,000. According to one embodiment, they have anumber-average molecular mass of greater than 5,600, for example,ranging from 5,700 to 99,000.

For the purposes of the invention, the expression “crystallizable chainor block” means a chain or block which, if it was obtained alone, wouldchange from the amorphous state to the crystalline state reversibly,depending on whether one is above or below the melting point. For thepurposes of the invention, a “chain” is a group of atoms, which arependent or lateral relative to the polymer skeleton. A “block” is agroup of atoms belonging to the skeleton, this group constituting one ofthe repeating units of the polymer. The expression “crystallizablechain” means a chain containing at least six carbon atoms.

According to one embodiment, the crystallizable block(s) or chain(s) ofthe semi-crystalline polymers represent at least 30% of the total weightof each polymer and better still at least 40%. The semi-crystallinepolymers of the invention containing crystallizable blocks are block ormultiblock polymers. They may be obtained by polymerizing a monomercontaining reactive (or ethylenic) double bonds or by polycondensation.When the polymers of the invention are polymers containingcrystallizable side chains, these side chains are advantageously inrandom form.

According to one embodiment, the semi-crystalline polymers of theinvention are of synthetic origin. In addition, they may not comprise apolysaccharide skeleton. Generally, the crystallizable units (chains orblocks) of the semi-crystalline polymers according to the invention arederived from monomer(s) containing crystallizable block(s) or chain(s),used for the manufacture of the semi-crystalline polymers.

According to the invention, a semi-crystalline polymer with a lowmelting point is a semi-crystalline polymer with a melting temperatureof less than 50° C. and a semi-crystalline polymer with a high meltingpoint is a semi-crystalline polymer with a melting temperature at leastequal to 50° C.

According to the invention, the low-melting semi-crystalline polymer andthe high-melting semi-crystalline polymer are chosen from blockcopolymers comprising at least one crystallizable block and at least oneamorphous block, homopolymers and copolymers bearing at least onecrystallizable side chain per repeating unit, and mixtures thereof.

The semi-crystalline polymers that may be used in the invention may bechosen from, by way of non-limiting example:

-   block copolymers of polyolefins of controlled crystallization,    especially those whose monomers are described in EP-A-0 951 897 (the    disclosure of which is incorporated herein by reference);-   polycondensates, for example, those of aliphatic or aromatic    polyester type or of aliphatic/aromatic copolyester type;-   homopolymers and copolymers bearing at least one crystallizable side    chain and homopolymers and copolymers bearing in the skeleton at    least one crystallizable block, for instance those described in U.S.    Pat. No. 5,156,911 (the disclosure of which is incorporated herein    by reference);-   homopolymers and copolymers bearing at least one crystallizable side    chain, for example those bearing fluoro group(s), as described in    document WO-A-01/19333 (the disclosure of which is incorporated    herein by reference),    and mixtures thereof. In the last two cases, the crystallizable side    chain(s) or block(s) are hydrophobic.    A) Semi-crystalline Polymers Containing Crystallizable Side Chains

Suitable non-limiting examples include those defined in U.S. Pat. No.5,156,911 and WO-A-01/19333 (the disclosures of which are incorporatedby reference herein). They are homopolymers and copolymers comprisingfrom 50% to 100% by weight of units resulting from the polymerization ofone or more monomers bearing a crystallizable hydrophobic side chain.

-   -   These homopolymers and copolymers are of any nature, provided        that they meet the conditions mentioned previously.

They can result:

-   from the polymerization, especially the free-radical polymerization,    of one or more monomers containing reactive or ethylenic double    bond(s) with respect to a polymerization, namely a vinyl,    (meth)acrylic or allylic group,-   from the polycondensation of one or more monomers bearing    co-reactive groups (carboxylic acid, sulphonic acid, alcohol, amine    and isocyanate), such as, for example, polyesters, polyurethanes,    polyethers, polyureas and polyamides.

In general, these polymers are chosen especially from homopolymers andcopolymers resulting from the polymerization of at least one monomercontaining crystallizable chain(s) that may be represented by formula X:

with M representing an atom of the polymer skeleton, S representing aspacer, and C representing a crystallizable group.

The crystallizable chains “—S—C” may be aliphatic or aromatic, andoptionally fluorinated or perfluorinated. “S” represents a group chosenfrom (CH₂)_(n), (CH₂CH₂O)_(n), and (CH₂O), which may chosen from linear,branched, and cyclic groups, with n being an integer ranging from 0 to22. According to one embodiment, “S” is a linear group. According to oneaspect, “S” and “C” are different.

When the crystallizable chains “—S—C” are hydrocarbon-based aliphaticchains, they comprise hydrocarbon-based alkyl chains containing at least11 carbon atoms and not more than 40 carbon atoms, for example, not morethan 24 carbon atoms. They can be chosen from alkyl chains containing atleast 12 carbon atoms, for example C₁₄-C₂₄ alkyl chains. When they arefluoroalkyl or perfluoroalkyl chains, they contain at least sixfluorinated carbon atoms and, according to one aspect, at least 11carbon atoms, at least six of which carbon atoms are fluorinated.

As non-limiting examples of semi-crystalline polymers or copolymerscontaining crystallizable chain(s), mention may be made of thoseresulting from the polymerization of one or more of the followingmonomers: (meth)acrylates of saturated alkyls, with the alkyl groupbeing C₁₄-C₂₄,; perfluoroalkyl(meth)acrylates with a C₁₁-C₁₅perfluoroalkyl group; N-alkyl(meth)acrylamides with the alkyl groupbeing C₁₄ to C₂₄, with or without a fluorine atom; vinyl esterscontaining alkyl or perfluoro(alkyl) chains with the alkyl group beingC₁₄ to C₂₄ (with at least 6 fluorine atoms per perfluoroalkyl chain);vinyl ethers containing alkyl or perfluoro(alkyl) chains, with the alkylgroup being C₁₄ to C₂₄ and at least 6 fluorine atoms per perfluoroalkylchain; C₁₄ to C₂₄ alpha-olefins such as, for example, octadecene,;paraalkylstyrenes with an alkyl group containing from 12 to 24 carbonatoms; and mixtures thereof.

When the polymers result from a polycondensation, the hydrocarbon-basedand/or fluorinated crystallizable chains as defined above are borne by amonomer that may be a diacid, a diol, a diamine or a diisocyanate.

When the polymers that are the subject of the invention are copolymers,they additionally contain from 0 to 50% of groups Y or Z resulting fromthe copolymerization:

-   α) of Y which is a polar or non-polar monomer or a mixture of the    two:    -   When Y is a polar monomer, it is either a monomer bearing        polyoxyalkylenated groups (especially oxyethylenated and/or        oxypropylenated groups), a hydroxyalkyl (meth)acrylate, for        instance hydroxyethyl acrylate, (meth)acrylamide, an        N-alkyl(meth)acrylamide, an N,N-dialkyl(meth)acrylamide such as,        for example, N,N-diisopropylacrylamide or N-vinylpyrrolidone        (NVP), N-vinylcaprolactam, a monomer bearing at least one        carboxylic acid group, for instance (meth)acrylic acid, crotonic        acid, itaconic acid, maleic acid or fumaric acid, or bearing a        carboxylic acid anhydride group, for instance maleic anhydride,        and mixtures thereof.    -   When Y is a non-polar monomer, it may be an ester of the linear,        branched or cyclic alkyl (meth)acrylate type, a vinyl ester, an        alkyl vinyl ether, an alpha-olefin, styrene or styrene        substituted with a C₁ to C₁₀ alkyl group, for instance        α-methylstyrene, or a macromonomer of the polyorganosiloxane        type containing vinyl unsaturation.

In accordance with the present invention, the term “alkyl” means asaturated group, such as of C₈ to C₂₄, except where otherwise mentioned,and such as of C₁₄ to C₂₄.

-   β) of Z which is a polar monomer or a mixture of polar monomers. In    this case, Z has the same definition as the “polar Y” defined above.

According to one aspect, the semi-crystalline polymers containing acrystallizable side chain are alkyl (meth)acrylate oralkyl(meth)acrylamide homopolymers with an alkyl group as defined above,such as of C₁₄-C₂₄, copolymers of these monomers with a hydrophilicmonomer, for example those of different nature from (meth)acrylic acid,for instance N-vinylpyrrolidone or hydroxyethyl (meth)acrylate, andmixtures thereof.

B) Polymers Bearing in the Skeleton at least One Crystallizable Block

These polymers are especially block copolymers comprising at least twoblocks of different chemical nature, one of which is crystallizable.

-   The block polymers defined in U.S. Pat. No. 5,156,911 (the    disclosure of which is incorporated herein by reference) may be    used;-   Block copolymers of olefin or of cycloolefin containing a    crystallizable chain, for instance those derived from the block    polymerization of:    -   cyclobutene, cyclohexene, cyclooctene, norbornene (i.e.        bicyclo(2,2,1)-2-heptene), 5-methylnorbornene,        5-ethylnorbornene, 5,6-dimethylnorbornene,        5,5,6-trimethylnorbornene, 5-ethylidenenorbornene,        5-phenylnorbornene, 5-benzylnorbornene, 5-vinylnorbornene,        1,4,5,8-dimethano-1,2,3,4,4a,5,8a-octahydronaphthalene,        dicyclopentadiene, or mixtures thereof,    -   with ethylene, propylene, 1-butene, 3-methyl-1-butene, 1-hexene,        4-methyl-1-pentene, 1-octene, 1-decene or 1-eicosene, or        mixtures thereof,    -   copoly(ethylene/norbornene) blocks and        (ethylene/propylene/ethylidene-norbornene) block terpolymers.        Those resulting from the block copolymerization of at least two        C₂-C₁₆, for example C₂-C₁₂, further C₄-C₁₂ α-olefins, such as        those mentioned above, and block bipolymers of ethylene and of        1-octene, may also be used.-   The copolymers may be copolymers containing at least one    crystallizable block, the copolymer residue being amorphous (at room    temperature). These copolymers may also contain two crystallizable    blocks of different chemical nature. Suitable copolymers include    those that simultaneously contain at room temperature a    crystallizable block and an amorphous block that are both    hydrophobic and lipophilic, sequentially distributed; mention may be    made, for example, of polymers containing one of the crystallizable    blocks and one of the amorphous blocks below:    -   Block that is crystallizable by nature: a) polyester, for        instance poly(alkylene terephthalate), b) polyolefin, for        instance polyethylenes or polypropylenes.    -   Amorphous and lipophilic block, for instance amorphous        polyolefins or copoly(olefin)s such as poly(isobutylene),        hydrogenated polybutadiene or hydrogenated poly(isoprene).

As examples of such copolymers containing a crystallizable block and aseparate amorphous block, mention may be made of:

-   α) poly(ε-caprolactone)-b-poly(butadiene) block copolymers, for    example used hydrogenated, such as those described in the article    “Melting Behavior of Poly(ε-caprolactone)-block-polybutadiene    copolymers” from S. Nojima, Macromolecules, 32, 3727-3734 (1999)    (the disclosure of which is incorporated herein by reference)-   β) the hydrogenated block or multiblock poly(butylene    terephthalate)-b-poly(isoprene) block copolymers cited in the    article “Study of Morphological and Mechanical Properties of PP/PBT”    by Boutevin et al., Polymer Bulletin, 34, 117-123 (1995) (the    disclosure of which is incorporated by reference herein),-   γ) the poly(ethylene)-b-copoly(ethylene/propylene) block copolymers    cited in the articles “Morphology of Semi-Crystalline Block    Copolymers of ethylene-(ethylene-alt -propylene)” by P. Rangarajan    et al., Macromolecules, 26, 4640-4645 (1993) and “Polymer Aggregates    with Crystalline Cores: the System    poly(ethylene)-poly(ethylene-propylene)” by P. Richter et al.,    Macromolecules, 30, 1053-1068 (1997),-   δ) the poly(ethylene)-b-poly(ethylethylene) block copolymers cited    in the general article “Crystallization in Block Copolymers”    by I. W. Hamley, Advances in Polymer Science, Vol. 148,    113-137 (1999) (the disclosures of which are all incorporated by    reference herein).

The semi-crystalline polymers in the composition of the invention may ormay not be partially crosslinked, provided that the degree ofcrosslinking does not interfere with their dissolution or dispersion inthe liquid fatty phase by heating above their melting point. It may thenbe a chemical crosslinking, by reaction with a multifunctional monomerduring the polymerization. It may also be a physical crosslinking whichmay, in this case, be due either to the establishment of bonds ofhydrogen or dipolar type between groups borne by the polymer, such as,for example, the dipolar interactions between carboxylate ionomers,these interactions being of small amount and borne by the polymerskeleton; or to a phase separation between the crystallizable blocks andthe amorphous blocks borne by the polymer.

According to one aspect, the semi-crystalline polymers in thecomposition according to the invention are non-crosslinked.

According to one embodiment of the invention, the polymer is chosen fromcopolymers resulting from the polymerization of at least one monomercontaining a crystallizable chain chosen from saturated C₁₄ to C₂₄ alkyl(meth)acrylates; C₁₁ to C₁₅ perfluoroalkyl (meth)acrylates; C₁₄ to C₂₄N-alkyl(meth)acrylamides substituted or unsubstituted with at least onefluorine atom, vinyl esters containing C₁₄ to C₂₄ alkyl orperfluoroalkyl chains, vinyl ethers comprising chains chosen from C₁₄ toC₂₄ alkyl and perfluoroalkyl chains, C₁₄ to C₂₄ alpha-olefins,para-alkylstyrenes with an alkyl group containing from 12 to 24 carbonatoms, with at least one optionally fluorinated C₁ to C₁₀ monocarboxylicacid ester or amide, which may be represented by the following formula:

in which R₁ is chosen from H and CH₃, R is chosen from optionallyfluorinated C₁-C₁₀ alkyl groups and X is chosen from O, NH, and NR₂ inwhich R₂ is chosen from optionally fluorinated C₁-C₁₀ alkyl groups.

According to one embodiment of the invention, the polymer is derivedfrom a monomer containing a crystallizable chain, chosen from saturatedC₁₄ to C₂₂ alkyl (meth)acrylates.

For example, the semi-crystalline polymer present in the compositionaccording to the invention may not be a polycaprolactone.

As suitable non-limiting examples of the structuring semi-crystallinepolymers that may be used in the composition according to the invention,mention may be made of the products Intelimer® from the company Landec,described in the brochure “Intelimer® polymers”, Landec IP22 (Rev. 4-97)(the disclosure of which is incorporated by reference herein). Thesepolymers are in solid form at room temperature (25° C.). They bearcrystallizable side chains and have the formula X above.

The semi-crystalline polymers may be:

-   those described in Examples 3, 4, 5, 7, 9 and 13 of U.S. Pat. No.    5,156,911 (the disclosure of which is incorporated by reference    herein) containing a —COOH group, resulting from the    copolymerization of acrylic acid and of C₅ to C₁₆ alkyl    (meth)acrylate and, for example, the copolymerization:    -   of acrylic acid, of hexadecyl acrylate and of isodecyl acrylate        in a 1/16/3 weight ratio,    -   of acrylic acid and of pentadecyl acrylate in a 1/19 weight        ratio,    -   of acrylic acid, of hexadecyl acrylate and of ethyl acrylate in        a 2.5/76.5/20 weight ratio,    -   of acrylic acid, of hexadecyl acrylate and of methyl acrylate in        a 5/85/10 weight ratio,    -   of acrylic acid and of octadecyl methacrylate in a 2.5/97.5        weight ratio,    -   of hexadecyl acrylate, of polyethylene glycol methacrylate        monomethyl ether containing 8 ethylene glycol units, and of        acrylic acid in an 8.5/1/0.5 weight ratio.

It is also possible to use the structure “O” from National Starch, asdescribed in U.S. Pat. No. 5,736,125, (the disclosure of which isincorporated herein by reference) with a melting point of 44° C., andalso semi-crystalline polymers with crystallizable pendent chainscomprising fluoro groups, as described in Examples 1, 4, 6, 7 and 8 ofWO-A-01/19333.

It is also possible to use low-melting semi-crystalline polymersobtained by copolymerization of stearyl acrylate and of acrylic acid orof NVP, as described in document U.S. Pat. No. 5,519,063 or EP-A-550,745(the disclosures of which are incorporated herein by reference), as wellas those described in Examples 1 and 2 below, for the preparation ofpolymers, with a melting point of 40° C. and 38° C., respectively.

It is also possible to use semi-crystalline polymers obtained bycopolymerization of behenyl acrylate and of acrylic acid or of NVP, asdescribed in U.S. Pat. No. 5,519,063 and EP-A-550 745, and as well asthose described in Examples 3 and 4 below, for the preparation ofpolymers, with a melting point of 60° C. and 58° C., respectively.

According to one embodiment, the low-melting semi-crystalline polymersand/or those with a high melting point do not comprise a carboxylicgroup.

According to embodiment, the composition also comprises a film-formingpolymer capable of forming a hydrophobic film, also known as the secondfilm-forming polymer.

The expression “film-forming polymer capable of forming a hydrophobicfilm” means a polymer whose film has a solubility in water at 25° C. ofless than 1% by weight.

The second film-forming polymer may be chosen from synthetic polymers,for example free-radical polymers or polycondensates, and polymers ofnatural origin, and mixtures thereof.

The term “free-radical film-forming polymer” means a polymer obtained bypolymerization of monomers containing unsaturation, especially ethylenicunsaturation (unlike polycondensates).

The film-forming polymers of free-radical type may include vinylpolymers or copolymers, for example acrylic polymers.

The vinyl film-forming polymers may result from the polymerization ofmonomers with ethylenic unsaturation containing at least one acidicgroup and/or esters of these acid monomers and/or amides of these acidmonomers.

As monomers bearing an acidic group, it is possible to use α,β-ethylenicunsaturated carboxylic acids such as acrylic acid, methacrylic acid,crotonic acid, maleic acid or itaconic acid. According to oneembodiment, (Meth)acrylic acid and crotonic acid are used, and accordingto another embodiment, (meth)acrylic acid.

The esters of acid monomers are advantageously chosen from (meth)acrylicacid esters (also referred to as (meth)acrylates), for example alkyl(meth)acrylates, including alkyl (meth)acrylates of a C₁-C₃₀ alkyl,which may be linear, branched or cyclic, for example C₁-C₂₀, aryl(meth)acrylates, for example of a C₆-C₁₀ aryl, and hydroxyalkyl(meth)acrylates, for example of a C₂-C₆ hydroxyalkyl.

Among the alkyl (meth)acrylates that may be mentioned are methylmethacrylate, ethyl methacrylate, butyl methacrylate, isobutylmethacrylate, 2-ethylhexyl methacrylate, lauryl methacrylate andcyclohexyl methacrylate.

Among the hydroxyalkyl (meth)acrylates that may be mentioned arehydroxyethyl acrylate, 2-hydroxypropyl acrylate, hydroxyethylmethacrylate and 2-hydroxypropyl methacrylate.

Among the aryl (meth)acrylates that may be mentioned are benzyl acrylateand phenyl acrylate.

The (meth)acrylic acid esters that are suitable include the alkyl(meth)acrylates.

According to the present invention, the alkyl group of the esters may beeither fluorinated or perfluorinated, that is to say that some or all ofthe hydrogen atoms of the alkyl group are replaced with fluorine atoms.

Non-limiting examples of amides of the acid monomers that may bementioned include (meth)acrylamides for exampleN-alkyl(meth)acrylamides, including those of a C₁-C₂₀ alkyl. Among theN-alkyl(meth)acrylamides that may be mentioned are N-ethylacrylamide,N-t-butylacrylamide, N-t-octylacrylamide and N-undecylacrylamide.

The vinyl film-forming polymers may also result from thehomopolymerization or copolymerization of at least one monomer chosenfrom vinyl esters, olefins (including fluoroolefins), vinyl ethers andstyrene monomers. These monomers may be polymerized with acid monomersand/or esters thereof and/or amides thereof, such as those mentionedabove.

Non-limiting examples of vinyl esters that may be mentioned are vinylacetate, vinyl neodecanoate, vinyl pivalate, vinyl benzoate and vinylt-butylbenzoate.

Suitable non-limiting examples of olefins that may be mentioned includeethylene, propylene, butene, isobutene, octene, octadecene, andpoly(fluorinated olefins), such as tetrafluoroethylene, vinylidenefluoride, hexafluoropropene or chlorotrifluoroethylene.

Styrene monomers that may be mentioned are styrene and α-methylstyrene.

The list of monomers given is not limiting and it is possible to use anymonomer known to those skilled in the art that fails within thecategories of acrylic and vinyl monomers (including monomers modifiedwith a silicone chain).

Among the polycondensates that may be used as a film-forming polymer,mention may thus be made of anionic, cationic, nonionic or amphotericpolyurethanes, polyurethane-acrylics,polyurethane-polyvinylpyrrolidones, polyester-polyurethanes,polyether-polyurethanes, polyureas and polyurea/polyurethanes, andmixtures thereof.

The film-forming polyurethane may be, for example, an aliphatic,cycloaliphatic or aromatic polyurethane, polyurea/urethane or polyureacopolymer, comprising, alone or as a mixture:

-   -   at least one sequence of aliphatic and/or cycloaliphatic and/or        aromatic polyester origin, and/or    -   at least one branched or unbranched silicone block, for example        polydimethylsiloxane or polymethylphenylsiloxane, and/or    -   at least one block comprising fluorinated groups.

Suitable examples of film-forming polycondensates that may also bementioned include polyesters, polyesteramides, fatty-chain polyesters,polyamides and epoxyester resins, resins resulting from the condensationof formaldehyde with an arylsulphonamide, and arylsulphonamide-epoxyresins.

The polyesters may be obtained, in a known manner, by polycondensationof dicarboxylic acids with polyols, for example diols.

The dicarboxylic acid may be aliphatic, alicyclic or aromatic.Non-limiting examples of such acids which may be mentioned include:oxalic acid, malonic acid, dimethylmalonic acid, succinic acid, glutaricacid, adipic acid, pimelic acid, 2,2-dimethylglutaric acid, azelaicacid, suberic acid, sebacic acid, fumaric acid, maleic acid, itaconicacid, phthalic acid, dodecanedioic acid, 1,3-cyclohexanedicarboxylicacid, 1,4-cyclohexanedicarboxylic acid, isophthalic acid, terephthalicacid, diglycolic acid, thiodipropionic acid, 2,5-naphthalenedicarboxylicacid or 2,6-naphthalenedicarboxylic acid. These dicarboxylic acidmonomers may be used alone or as a combination of at least twodicarboxylic acid monomers. Among these monomers, the ones suitablychosen include phthalic acid, isophthalic acid and terephthalic acid.

The diol may be chosen from aliphatic, alicyclic and aromatic diols. Thediol used may be chosen from: ethylene glycol, diethylene glycol,triethylene glycol, 1,3-propanediol, cyclohexanedimethanol and4-butanediol. Other polyols that may be used are glycerol,pentaerythritol, sorbitol and trimethylolpropane.

The polyesteramides may be obtained in a manner similar to that of thepolyesters, by polycondensation of diacids with diamines or with aminoalcohols. Diamines that may be used include ethylenediamine,hexamethylenediamine, meta-phenylenediamine and para-phenylenediamine.An amino alcohol that may be used is monoethanolamine.

The polyester may also comprise at least one monomer bearing at leastone group —SO₃M, with M being chosen from a hydrogen atom, an ammoniumion NH₄ ⁺ and a metal ion such as, for example, an Na⁺, Li⁺, K⁺, Mg²⁺,Ca²⁺, Cu²⁺, Fe²⁺ or Fe³⁺ ion. A difunctional aromatic monomer comprisingsuch a group —SO₃M may also be used.

The aromatic nucleus of the difunctional aromatic monomer also bearing agroup —SO₃M as described above may be chosen, for example, from benzene,naphthalene, anthracene, biphenyl, oxybiphenyl, sulphonylbiphenyl andmethylenebiphenyl nuclei. Examples of difunctional aromatic monomersalso bearing a group —SO₃M that may be mentioned include:sulphoisophthalic acid, sulphoterephthalic acid, sulphophthalic acid,4-sulphonaphthalene-2,7-dicarboxylic acid.

In the compositions which are the subject of the invention, it ispossible to use copolymers based on isophthalate/sulphoisophthalate, aswell as copolymers obtained by condensation of di-ethylene glycol,cyclohexanedimethanol, isophthalic acid or sulphoisophthalic acid. Suchpolymers are sold, for example, under the brand name Eastman AQ by thecompany Eastman Chemical Products.

The synthetic hydrophobic polymer may also be a silicone polymer, forexample polyorganopolysiloxane.

The polymers of natural origin, which are optionally modified, may bechosen from shellac resin, sandarac gum, dammar resins, elemi resins,copal resins, cellulose polymers such as nitrocellulose, celluloseacetate, cellulose acetobutyrate, cellulose acetopropionate orethylcellulose, and mixtures thereof.

Film-forming polymers that may also be used are film-forming siliconepolymers.

According to one embodiment of the invention, the second polymer may bepresent in the form of solid particles dispersed in an aqueous medium.The expression “polymer in the form of particles in aqueous dispersion”,which is generally known as a latex or pseudolatex, means a phasecontaining water and optionally a water-soluble compound, in which isdirectly dispersed the polymer in the form of particles.

The size of the polymer particles in aqueous dispersion may range from10 nm to 500 nm, for example from 20 nm to 300 nm.

The aqueous medium may consist essentially of water or may also comprisea mixture of water and of water-miscible solvent, for instance lowermonoalcohols containing from 1 to 5 carbon atoms, glycols containingfrom 2 to 8 carbon atoms, C₃-C₄ ketones or C₂-C₄ aldehydes. In practice,it represents from 5% to 94.9% by weight relative to the total weight ofthe composition.

Suitable non-limiting examples of film-forming polymers in aqueousdispersion which may be used include the acrylic polymers sold under thenames Neocryl XK-90®, Neocryl A-1070®, Neocryl A-1090®, Neocryl BT-62®,Neocryl A-1079® and Neocryl A-523® by the company Avecia-Neoresins, DowLatex 432® by the company Down Chemical, or polyurethanes such as thepolyester-polyurethanes sold under the names “Avalure UR-405®”, “AvalureUR-410®”, “Avalure UR-425®” and “Sancure 2060®” by the company Goodrich,the polyether-polyurethanes sold under the names “Sancure 878®” and“Avalure UR-450®” by the company Goodrich and “Neorez R 970®” by thecompany ICI and the polyurethane-acrylics sold under the name NeorezR-989® by the company Avecia-Neoresins.

It is also possible to use “alkali-soluble” polymers, taking care toensure that the pH of the composition is adjusted so as to keep thesepolymers in the form of particles in aqueous dispersion.

The composition according to the invention may comprise a film-formingauxiliary agent that promotes the formation of a film with the particlesof the film-forming polymer. Such a film-forming agent may be chosenfrom any compounds known to those skilled in the art as being capable offulfilling the desired function, and may be chosen in particular fromplasticizers and coalescers.

According to a second embodiment variant of the invention, the secondfilm-forming polymer, also known as the liposoluble polymer, may bepresent in dissolved form in a liquid fatty phase.

Non-limiting examples of liposoluble polymers that may be mentionedinclude polymers corresponding to formula (I) below:

in which:

-   R₁ represents a linear or branched saturated hydrocarbon-based chain    containing from 1 to 19 carbon atoms;-   R₂ represents a radical taken from the group consisting of:    -   a) —O—CO—R₄, R₄ having the same meaning as R₁ but is different        from R₁ in the same copolymer,    -   b) —CH₂—R₅, R₅ representing a linear or branched saturated        hydrocarbon-based chain containing from 5 to 25 carbon atoms,    -   c) —O—R₆, R₆ representing a saturated hydrocarbon-based chain        containing from 2 to 18 carbon atoms, and    -   d) —CH₂—O—CO—R₇, R₇ representing a linear or branched saturated        hydrocarbon-based chain containing from 1 to 19 carbon atoms,-   R₃ represents a hydrogen atom when R₂ represents the radicals a), b)    or c) or R₃ represents a methyl radical when R₂ represents a radical    d), the said copolymer needing to consist of at least 15% by weight    of at least one monomer derived from a unit (Ia) or from a unit (Ib)    in which the saturated or branched hydrocarbon-based chains contain    at least 7 carbon atoms.

The copolymers of formula (I) result from the copolymerization of atleast one vinyl ester (corresponding to the unit Ia) and of at least oneother monomer (corresponding to the unit Ib), which may be an α-olefin,an alkyl vinyl ether or an allylic or methallylic ester.

When, in the unit (Ib), R₂ is chosen from the radicals —CH₂—R₅, —O—R₆ or—CH₂—O—CO—R₇ as defined above, the copolymer of formula (I) may consistof from 50 mol % to 95 mol % of at least one unit (Ia) and of from 5 mol% to 50 mol % of at least one unit (Ib).

The copolymers of formula (I) may also result from the copolymerizationof at least one vinyl ester and of at least one other vinyl ester thatis different from the first ester. In this case, these copolymers mayconsist of from 10 mol % to 90 mol % of at least one unit (Ia) and offrom 10 mol % to 90 mol % of at least one unit (Ib) in which R₂represents a radical —O—CO—R₄.

Among the vinyl esters leading to the unit of formula (Ia), or to theunit of formula (Ib) in which R₂=—O—CO—R₄, mention may be made of vinylacetate, vinyl propionate, vinyl butanoate, vinyl octanoate, vinyldecanoate, vinyl laurate, vinyl stearate, vinyl isostearate, vinyl2,2-dimethyloctanoate and vinyl dimethylpropionate.

Among the α-olefins leading to the unit of formula (Ib) in whichR₂=—CH₂—R₅, mention may be made of 1-octene, 1-dodecene, 1-octadeceneand 1-eicosene, and mixtures of α-olefins containing from 22 to 28carbon atoms.

Among the alkyl vinyl ethers leading to the unit of formula (Ib) inwhich R₂=—O—R₆, mention may be made of ethyl vinyl ether, n-butyl vinylether, isobutyl vinyl ether, decyl vinyl ether, dodecyl vinyl ether,cetyl vinyl ether and octadecyl vinyl ether.

Among the allylic or methallylic esters leading to the unit of formula(Ib) in which R₂=—CH₂—O—CO—R₇, mention may be made of allyl andmethallyl acetates, propionates, dimethylpropionates, butyrates,hexanoates, octanoates, decanoates, laurates, 2,2-dimethylpentanoates,stearates and eicosanoates.

The copolymers of formula (I) may also be crosslinked using certaintypes of crosslinking agents that are intended to substantially increasetheir molecular weight.

This crosslinking is carried out during the copolymerization and thecrosslinking agents may be either of the vinyl type or of the allylic ormethallylic type. Among these crosslinking agents that may be mentionedare tetraallyloxyethane, divinylbenzene, divinyl octanedioate, divinyldodecanedioate and divinyl octadecanedioate.

Among the various copolymers of formula (I) which may be used in thecomposition according to the invention, mention may be made of thefollowing copolymers: vinyl acetate/allyl stearate, vinyl acetate/vinyllaurate, vinyl acetate/vinyl stearate, vinyl acetate/octadecene, vinylacetate/octadecyl vinyl ether, vinyl propionate/allyl laurate, vinylpropionate/vinyl laurate, vinyl stearate/l-octadecene, vinylacetate/1-dodecene, vinyl stearate/ethyl vinyl ether, vinylpropionate/cetyl vinyl ether, vinyl stearate/allyl acetate, vinyl2,2-dimethyloctanoate/vinyl laurate, allyl 2,2-dimethylpentanoate/vinyllaurate, vinyl dimethylpropionate/vinyl stearate, allyldimethylpropionate/vinyl stearate, vinyl propionate/vinyl stearate,crosslinked with 0.2% divinylbenzene, vinyl dimethylpropionate/vinyllaurate, crosslinked with 0.2% divinylbenzene, vinyl acetate/octadecylvinyl ether, crosslinked with 0.2% tetraallyloxyethane, vinylacetate/allyl stearate, crosslinked with 0.2% divinylbenzene, vinylacetate/1-octadecene, crosslinked with 0.2% divinylbenzene, and allylpropionate/allyl stearate, crosslinked with 0.2% divinylbenzene.

Liposoluble film-forming polymers which may also be mentioned includeliposoluble homopolymers, for example those resulting from thehomopolymerization of vinyl esters containing from 9 to 22 carbon atomsor of alkyl acrylates or methacrylates, the alkyl radicals containingfrom 10 to 20 carbon atoms.

Such liposoluble homopolymers may be chosen from polyvinyl stearate,polyvinyl stearate crosslinked with divinylbenzene, with diallyl etheror with diallyl phthalate, polystearyl (meth)acrylate or polylauryl(meth)acrylate, these poly(meth)acrylates possibly being crosslinkedwith the aid of ethylene glycol dimethacrylate or tetraethylene glycoldimethacrylate.

The liposoluble copolymers and homopolymers defined above are known andare disclosed in, for example, patent application FR-A-2 262 303 (thedisclosure of which is incorporated by reference herein); they may havea weight-average molecular weight ranging from 2,000 to 500,000 andpreferably from 4,000 to 200,000.

As liposoluble film-forming polymers which may be used in the invention,mention may also be made of polyalkylenes and C₂-C₂₀ alkene copolymers,other than the polyolefin wax defined in a), for instance polybutene,alkylcelluloses with a linear or branched, saturated or unsaturated C₁to C₈ alkyl radical, for instance ethylcellulose and propylcellulose,vinylpyrrolidone (VP) copolymers and copolymers of vinylpyrrolidone andof C₂ to C₄₀, for example C₃ to C₂₀ alkene. As non-limiting examples ofVP copolymers that may be used in the invention, mention may be made ofVP/vinyl acetate, VP/ethyl methacrylate, butylated polyvinylpyrrolidone(PVP), VP/ethyl methacrylate/methacrylic acid, VP/hexadecene,VP/triacontene, VP/styrene or VP/acrylic acid/lauryl methacrylatecopolymer.

The liquid fatty phase may comprise a volatile liquid fatty phase,optionally as a mixture with a non-volatile liquid fatty phase.

The expression “volatile fatty phase” means any non-aqueous medium thatis capable of evaporating from the skin in less than one hour. Thisvolatile phase may comprise oils with a vapour pressure, at roomtemperature and atmospheric pressure, ranging from 10⁻³ to 300 mmHg(0.13 Pa to 40 000 Pa).

The liquid fatty phase in which the polymer is dispersed may becomprised of any physiologically acceptable and cosmetically acceptableoil chosen from, for example, oils of mineral, animal, plant orsynthetic origin, carbon-based oils, hydrocarbon-based oils, fluoro oilsand/or silicone oils, alone or as a mixture provided that they form ahomogeneous and stable mixture and provided that they are compatiblewith the intended use.

The total liquid fatty phase of the composition may range from 5% to 98%by weight relative to the total weight of the composition, for examplefrom 20% to 85% by weight. The non-volatile part may range from 0 to 80%(for example from 0.1% to 80%) of the total weight of the composition,and also from 1% to 50%.

As liquid fatty phase which may be used in the invention, mention maythus be made of fatty acid esters, higher fatty acids, higher fattyalcohols, polydimethylsiloxanes (PDMSs), which are optionally phenylatedsuch as phenyltrimethicones, or which are optionally substituted withaliphatic and/or aromatic groups, which may be fluorinated, or areoptionally substituted with functional groups such as hydroxyl, thioland/or amine groups; polysiloxanes modified with fatty acids, with fattyalcohols or with polyoxyalkylenes, fluorosilicones and perfluoro oils.

For example, one or more oils that are volatile at room temperature maybe used. After evaporating off these oils, a non-sticky, supplefilm-forming deposit is obtained. These volatile oils also make iteasier to apply the composition to keratin fibres such as the eyelashes.

These volatile oils can be hydrocarbon-based oils or silicone oilsoptionally comprising alkyl or alkoxy groups at the end of the siliconechain or pendent on the chain.

As volatile silicone oils which can be used in the invention, mentionmay be made of linear or cyclic silicones containing from 2 to 7 siliconatoms, these silicones optionally comprising alkyl or alkoxy groupscontaining from 1 to 10 carbon atoms. Mention may be made ofoctamethylcyclotetrasiloxane, decamethylcyclopentasiloxane,hexadecamethylcyclohexasiloxane, heptamethylhexyltrisiloxane andheptamethyloctyltrisiloxane.

Volatile hydrocarbon-based oils that may be mentioned include C₈-C₁₆isoparaffins such as Isopars and Permetyls, as well as isododecane.

These volatile oils can be present in the composition in an amountranging from 5% to 94.9% relative to the total weight of thecomposition, for example from 20% to 85%.

The second film-forming polymer may be present in a solids contentranging from 5% to 60% by weight relative to the total weight of thecomposition, for example from 10% to 45% by weight, and also from 15% to35% by weight.

For example, the first semi-crystalline polymer and the secondfilm-forming polymer may be present in the composition in a secondfilm-forming polymer/first semi-crystalline polymer weight ratio rangingfrom 90/10 to 10/90, such as from 70/30 to 30/70 and further such asfrom 60/40 to 40/60.

The composition may also comprise at least one dyestuff, for instancepulverulent compounds and/or liposoluble dyes, for example in aproportion of from 0.01% to 50% relative to the total weight of thecomposition. The pulverulent compounds may be chosen from the pigmentsand/or nacres usually used in cosmetic compositions. For example, thepulverulent compounds represent from 0.1% to 25% of the total weight ofthe composition, such as from 1% to 20%.

The pigments may be white or colored, and mineral and/or organic. Amongthe mineral pigments which may be mentioned are titanium dioxide,optionally surface-treated, zirconium oxide and cerium oxide, and alsoiron oxide, chromium oxide, manganese violet, ultramarine blue, chromiumhydrate and ferric blue. Among the organic pigments that may bementioned are carbon black, pigments of D & C type and lakes based oncochineal carmine or on barium, strontium, calcium or aluminium.

The nacreous pigments may be chosen from white nacreous pigments such asmica coated with titanium or with bismuth oxychloride, colored nacreouspigments such as titanium mica with iron oxides, titanium mica with,ferric blue or with chromium oxide, titanium mica with an organicpigment of the abovementioned type, and also nacreous pigments based onbismuth oxychloride.

The composition may also comprise fillers, which may be chosen fromthose that are well known to those skilled in the art and which arecommonly used in cosmetic compositions. The fillers may be mineral ororganic, and lamellar or spherical. Mention may be made of talc, mica,silica, kaolin, Nylon powder (Orgasol from Atochem), poly-β-alaninepowder, polyethylene powder, Teflon, lauroyllysine, starch, boronnitride, tetrafluoroethylene polymer powders, hollow microspheres suchas Expancel (Nobel Industrie), Polytrap (Dow Corning), silicone resinmicrobeads (for example Tospearls from Toshiba), precipitated calciumcarbonate, magnesium carbonate, magnesium hydrocarbonate,hydroxyapatite, hollow silica microspheres (Silica Beads from Maprecos),glass or ceramic microcapsules, metal soaps derived from organiccarboxylic acids containing from 8 to 22, for example from 12 to 18carbon atoms, for example zinc stearate, magnesium stearate, lithiumstearate, zinc laurate or magnesium myristate.

The composition may also contain any additive usually used in suchcompositions, such as thickeners, preserving agents, fragrances,sunscreens, free-radical scavengers, waxes, oils, moisturizers,vitamins, proteins, plasticizers, sequestrants, ceramides, acidifying orbasifying agents, or emollients.

Needless to say, a person skilled in the art will take care to selectthis or these optional additional compound(s), and/or the amountthereof, such that the advantageous properties of the compositionaccording to the invention are not, or are not substantially, adverselyaffected by the addition envisaged.

The invention is illustrated in greater detail in the examples thatfollow.

Test to Measure the Water Resistance of a Film:

A layer of composition 300 μm thick (before drying) with an area of 9cm×9 cm is spread onto a glass plate with an area of 10 cm×10 cm, isleft to dry for 24 hours at 30° C. and 50% relative humidity. Afterdrying, the plate is placed in a crystallizing vessel with a diameter of19 cm and a volume of 2 liters filled with 1 liter of water, placed on amagnetic hotplate-stirrer sold under the name RCT basic by the companyIKA Labortechnik.

A smooth PTFE cylindrical magnetic bar (length 6 cm; diameter 1 cm) isthen placed on the film. The stirring speed is set to position 5. Thewater temperature is controlled using a thermometer at a temperature of20° C. or 40° C. At time t₀=0, stirring is started. The time t(expressed in minutes) after which the film begins to detach or loosenfrom the plate or when a hole the size of the magnetic stirring bar isobserved, i.e. when the hole has a diameter of 6 cm, is measured. Thetest is stopped if the film remains intact at the end of 2 hours. Thewater resistance of the film corresponds to the time t measured,expressed in minutes.

Test of Water Uptake of a Film:

A layer of composition 300 μm thick (before drying) placed on a plate isspread out and then dried for 24 hours at 30° C. and at 50% relativehumidity; pieces about 1 cm² cut out of the dry film are weighed (massmeasurement M1) and then immersed in water, at 20° C. or at 40° C., for10 minutes; after immersion, the piece of film is wiped to remove theexcess water from the surface and then weighed (mass measurement M2).The difference M2−M1 corresponds to the amount of water absorbed by thefilm.

The water uptake of the film is equal to [(M2−M1)/M1]×100 and isexpressed as a weight percentage of water relative to the weight of thefilm.

EXAMPLES OF MANUFACTURE OF SEMI-CRYSTALLINE POLYMERS Example 1 AcidicPolymer with a Melting Point of 40° C.

120 g of Parleam are placed in a 1 I reactor equipped with a centralpaddle stirrer, a condenser and a thermometer, and are heated from roomtemperature to 80° C. over 45 minutes. At 80° C., the following mixtureC₁ is introduced over 2 hours: 40 g of cyclohexane+4 g of Triganox 141[2,5-bis(2-ethylhexanoylperoxy)-2,5-dimethylhexane].

30 minutes after the start of the addition of the mixture C₁, themixture C₂ is introduced over 1 hour 30 minutes, consisting of: 190 g ofstearyl acrylate+10 g of acrylic acid +400 g of cyclohexane.

At the end of the two additions, the mixture is stirred for a further 3hours at 80° C. and all the cyclohexane present in the reaction mediumis then distilled off at atmospheric pressure.

The polymer is thus obtained at 60% by weight of active material inParleam. Its weight-average molecular mass M_(w) is 35 000, expressed aspolystyrene equivalent, and its melting point T_(m) is 40° C. ±1° C.,measured by DSC.

Example 2 Basic Polymer with a Melting Point of 38° C.

The same procedure as in Example 1 is applied, except thatN-vinylpyrrolidone is used instead of acrylic acid.

The polymer obtained is at 60% by weight of active material in Parleam,its weight-average molecular mass M_(w) is 38 000 and its T_(m) is 38°C.

Examples 3 and 4

The semi-crystalline polymers of Examples 1 and 2 were tested in thefollowing composition:

Polyurethane as an aqueous dispersion, sold under 14 g A.M. the nameAvalure UR 425 by the company Goodrich, at an active material content of49% by weight Semi-crystalline polymer 10 g A.M. Hydroxyethylcellulose1.9 g Black iron oxide 5 g Propylene glycol 5 g Preserving agents qsWater qs 100 g

For each composition, the resistance to cold water (20° C.) (noted asRES) and to warm water (40° C.), and the water uptake (noted as UPT) ofthe film at 20° C. and at 40° C., were measured in accordance with theprotocols described above.

The following results were obtained:

Example 3 4 Semi-crystalline Example 1 Example 2 polymer RES 20° C. 40100 (in minutes) RES 40° C. 3 15 (in minutes) UPT 20° C. 30.8 20.4 (in%) UPT 40° C. 54.5 32.5 (in %)

It is found that, for each composition, the film of makeup is much lessresistant in the presence of water at 40° C. (warm water) than in thepresence of water at room temperature (cold water). Furthermore, thefilm takes up more water at a temperature of 40° C. than at 20° C. Themakeup is thus resistant to cold water and is easy to remove with warmwater.

Each composition was also applied to the eyelashes: the makeup resultobtained is easy to remove with warm water (40° C.) in the form of asleeve.

Example 5

A mascara having the composition below was prepared:

Polyurethane as an aqueous dispersion, sold under 18 g A.M. the nameAvalure UR 425 by the company Goodrich, at an active material content of49% by weight Semi-crystalline polymer of Example 2 15 g A.M.Hydroxyethylcellulose 1.9 g Black iron oxide 5 g Propylene glycol 5 gPreserving agents qs Water qs 100 g

This composition forms a film having a resistance (noted as RES) to coldwater (20° C.) equal to 80 minutes, and a resistance to warm water (40°C.) equal to 12 minutes, measured in accordance with the protocoldescribed above.

It is found that the film of makeup obtained is much less resistant inthe presence of water at 40° C. (warm water) than in the presence ofwater at room temperature (cold water). The makeup is thus resistant tocold water and is easier to remove with warm water.

Each composition was also applied to the eyelashes: the makeup resultobtained is easy to remove with warm water (40° C.) in the form of asheath.

1. A composition comprising, in a physiologically acceptable medium, atleast one first semi-crystalline polymer having a melting point ofgreater than or equal to 30° C., and at least one second film-formingpolymer that is capable of forming a hydrophobic film at roomtemperature, wherein the at least one second film-forming polymer ispresent in an amount ranging from 5% to 60% by weight, relative to thetotal weight of the composition.
 2. The composition of claim 1, whereinthe at least one first semi-crystalline polymer has a melting paintranging from 30° C. to 80° C.
 3. The composition of claim 2, wherein theat least one first semi-crystalline polymer has a melting point rangingfrom 30° C. to 60° C.
 4. The composition of claim 1, wherein the atleast one first semi-crystalline polymer has a number-average molecularmass of greater than or equal to 1,000.
 5. The composition of claim 1,wherein the at least one first semi-crystalline polymer has anumber-average molecular mass ranging from 3,000 to 500,000.
 6. Thecomposition of claim 5, wherein the at least one first semi-crystallinepolymer has a number-average molecular mass ranging from 4,000 to150,000.
 7. The composition of claim 1, wherein the at least one firstsemi-crystalline polymer comprises i) a polymer skeleton; and ii) atleast one crystallizable side chain and/or at least one crystallizableorganic block that forms part of the skeleton of said at least one firstsemi-crystalline polymer.
 8. The composition of claim 1, wherein the atleast one first semi-crystalline polymer is chosen from block copolymerscomprising at least one crystallizable block and at least one amorphousblock, and homopolymers and copolymers bearing at least onecrystallizable side chain per repeating unit.
 9. The composition ofclaim 8, wherein in said block copolymers, there are at least twocrystallizable blocks that are not identical and/or there are at leasttwo amorphous blocks that are not identical.
 10. The composition ofclaim 1, wherein the at least one first semi-crystalline polymer ischosen from: block copolymers of polyolefins of controlledcrystallization; aliphatic and aromatic polyester polycondensates andaliphatic/aromatic copolyesters; and homopolymers and copolymers bearingat least one crystallizable side chain.
 11. The composition of claim 1,wherein the at least one first semi-crystalline polymer is chosen fromhomopolymers and copolymers comprising from 50% to 100% by weight ofunits resulting from the polymerization of at least one monomer bearingat least one crystallizable hydrophobic side chain.
 12. The compositionof claim 1, wherein the at least one first semi-crystalline polymer ischosen from block homopolymers and copolymers resulting from thepolymerization of at least one monomer comprising at least one amorphousblock, and at least one crystallizable side chain per repeating unit, offormula X:

wherein M represents an atom of a polymer skeleton, S represents aspacer, C represents a crystallizable group, and “—S—C” is chosen fromoptionally fluorinated and perfluorinated alkyl chains comprising atleast 11 carbon atoms.
 13. The composition of claim 1, wherein the atleast one first semi-crystalline polymer is chosen from polymersresulting from the polymerization of at least one monomer chosen fromacrylic acid, methacrylic acid, crotonic acid, itaconic acid, maleicacid, and maleic anhydride.
 14. The composition of claim 1, wherein theat least one first semi-crystalline polymer is chosen from homopolymersand copolymers resulting from the polymerization of at least one monomercomprising a crystallizable block, chosen from saturated C₁₄-C₂₄ alkyl(meth)acrylates; C₁₁-C₁₅ perfluoroalkyl (meth)acrylates; C₁₄ to C₂₄N-alkyl(meth)acrylamides unsubstituted or substituted with at least onefluorine atom; vinyl esters comprising chains chosen from C₁₄ to C₂₄alkyl and perfluoroalkyl chains; vinyl ethers comprising chains chosenfrom C₁₄ to C₂₄ alkyl and perfluoroalkyl chains; C₁₄ to C₂₄alpha-olefins; and para-alkylstyrenes with an alkyl group comprisingfrom 12 to 24 carbon atoms.
 15. The composition of claim 1, wherein theat least one first semi-crystalline polymer is chosen from copolymersresulting from the polymerization of at least one monomer containing acrystallizable chain, chosen from saturated C₁₄ to C₂₄ alkyl(meth)acrylates; C₁₁ to C₁₅ perfluoroalkyl(meth)acrylates; C₁₄ to C₂₄N-alkyl(meth)acrylamides unsubstituted or substituted with at least onefluorine atom; vinyl esters comprising chains chosen from C₁₄ to C₂₄alkyl and perfluoroalkyl chains; vinyl ethers comprising chains chosenfrom C₁₄ to C₂₄ alkyl and perfluoroalkyl chains; C₁₄ to C₂₄alpha-olefins; and para-alkylstyrenes with an alkyl group comprisingfrom 12 to 24 carbon atoms with at least one monomer chosen fromoptionally fluorinated C₁ to C₁₀ monocarboxylic acid ester and amides.16. The composition of claim 1, wherein the at least one firstsemi-crystalline polymer is chosen from C₁₄ to C₂₄ alkyl(meth)acrylateand C₁₄ to C₂₄ alkyl(meth)acrylamide homopolymers, and copolymers of atleast one monomer chosen from C₁₄ to C₂₄ alkyl(meth)acrylate and C₁₄ toC₂₄ alkyl(meth)acrylamide homopolymers with at least one hydrophilicmonomer.
 17. The composition of claim 1, wherein the at least one firstsemi-crystalline polymer is chosen from copolymers of at least onemonomer chosen from C₁₄ to C₂₄ alkyl(meth)acrylate and C₁₄ to C₂₄alkyl(meth)acrylamide, with at least one hydrophilic monomer that is notidentical to (meth)acrylic acid.
 18. The composition of claim 17,wherein the at least one hydrophilic monomer is chosen fromN-vinylpyrrolidone and hydroxyethyl (meth)acrylate.
 19. The compositionof claim 1, wherein the at least one first semi-crystalline polymer isderived from a monomer containing a crystallizable chain chosen fromsaturated C₁₄ to C₂₂ alkyl(meth)acrylates.
 20. The composition of claim1, wherein the at least one first semi-crystalline polymer has acrystallizable organic chain and/or a crystallizable block representingat least 30% of the total weight of the polymer.
 21. The composition ofclaim 1, wherein the at least one first semi-crystalline polymer ispresent in an amount ranging from 0.1% to 30% by weight, relative to thetotal weight of the composition.
 22. The composition of claim 21,wherein the at least one first semi-crystalline polymer is present in anamount ranging from 0.5% to 25% by weight, relative to the total weightof the composition.
 23. The composition of claim 22, wherein the atleast one first semi-crystalline polymer is present in an amount rangingfrom 1% to 20% by weight, relative to the total weight of thecomposition.
 24. The composition of claim 1, wherein the at least onesecond film-forming polymer is chosen from free-radical polymers,polycondensates and polymers of natural origin.
 25. The composition ofclaim 1, wherein the at least one second film-forming polymer is chosenfrom vinyl polymers, polyurethanes, polyesters, and cellulose polymers.26. The composition of claim 1, wherein the at least one secondfilm-forming polymer is in a form of solid particles in aqueousdispersion.
 27. The composition of claim 1, wherein the at least onesecond film-forming polymer is a polyurethane in a form of particles inan aqueous dispersion.
 28. The composition of claim 1, wherein the atleast one second film-forming polymer is dissolved in a liquid fattyphase.
 29. The composition of claim 28, wherein the liquid fatty phasecomprises at least one oil chosen from hydrocarbon-based oils, fluorooils, and silicone oils of mineral, animal, plant and synthetic origin.30. The composition of claim 28, wherein the liquid fatty phasecomprises at least one oil that is volatile at room temperature.
 31. Thecomposition of claim 1, wherein the at least one second film-formingpolymer is present in an amount ranging from 10% to 45% by weight,relative to the total weight of the composition.
 32. The composition ofclaim 31, wherein the at least one second film-forming polymer ispresent in an amount ranging from 15% to 35% by weight, relative to thetotal weight of the composition.
 33. The composition of claim 1, whereinthe at least one first semi-crystalline polymer and the at least onesecond film-forming polymer are present in said composition in an atleast one second film-forming polymer/at least one firstsemi-crystalline polymer weight ratio ranging from 90:10 to 10:90. 34.The composition of claim 33, wherein said ratio ranges from 70:30 to30:70.
 35. The composition of claim 34, wherein said ratio ranges from60:40 to 40:60.
 36. The composition of claim 1, further comprising atleast one additive chosen from thickeners, dyestuffs, preserving agents,fragrances, sunscreens, free-radical scavengers, waxes, oils,moisturizers, vitamins, proteins, plasticizers, sequestrants, ceramides,acidifying and basifying agents, and emollients.
 37. The composition ofclaim 1, wherein said composition is in a form chosen from a mascara, aneyeliner, a product for the lips, a face powder, an eyeshadow, afoundation, a makeup product for the body, a concealer product, aproduct for the nails, an antisun composition, a skin coloringcomposition and a skincare product.
 38. A mascara comprising, in aphysiologically acceptable medium, at least one first semi-crystallinepolymer with a melting point of greater than or equal to 30° C., and atleast one second film-forming polymer capable of forming a hydrophobicfilm at room temperature.
 39. A process for making up or caring for akeratin material, comprising applying to said keratin material acomposition according to claim
 1. 40. A process for preparing a filmcomprising applying the composition of claim 1 to a keratinous material,wherein said film is more resistant to removal by cold water than toremoval by warm water.
 41. A process for making a film comprisingincluding in a cosmetic makeup or care composition for a keratinmaterial at least one first semi-crystalline polymer with a meltingpoint of greater than or equal to 30° C. and at least one secondfilm-forming polymer capable of forming a hydrophobic film at roomtemperature; wherein said film is applied to said keratin material andis more resistant to removal by cold water than to removal by warm waterhaving a temperature of at least 35° C.
 42. A process for removingmakeup from a keratin material comprising: (i) applying the compositionof claim 1 to said keratin material; and (ii) contacting the resultantkeratin material after step (i) with warm water at a temperature rangingfrom 35° C. to 50° C.; wherein step (ii) is optionally repeated.
 43. Theprocess of claim 41, wherein the warm water does not contain adetergent.
 44. A composition comprising, in a physiologically acceptablemedium, at least one first semi-crystalline polymer having a meltingpoint of greater than or equal to 30° C., and at least one secondfilm-forming polymer that is capable of forming a hydrophobic film atroom temperature; wherein said at least one semi-crystalline polymerdoes not comprise a polysaccharide backbone, wherein the at least onesecond film-forming polymer is present in an amount ranging from 5% to60% by weight, relative to the total weight of the composition.
 45. Acomposition comprising, in a physiologically acceptable medium, at leastone first semi-crystalline polymer having a melting point of greaterthan or equal to 30° C., and at least one second film-forming polymerthat is capable of forming a hydrophobic film at room temperature;wherein said semi-crystalline polymer is not polycaprolactone, whereinthe at least one second film-forming polymer is present in an amountranging from 5% to 60% by weight, relative to the total weight of thecomposition.